Reversible-Deactivation Radical Polymerisation: chain polymerisation made simple

Reversible-Deactivation Radical Polymerisation (RDRP) is one of the most exciting developments in chemistry over the past few decades, but it is rarely mentioned when polymerisation mechanisms are introduced in the final years of secondary education or first years of tertiary education. We propose that this is unfortunate, as RDRP is simpler than conventional Radical Polymerisation both conceptually and in terms of setting quantitative problems, and that it illustrates several other important features of chemistry as a human endeavour: How essential mechanistic unities are hidden by the details of how we write a chemical reaction, how a ‘bug’ in one stage of development of a process can become a ‘feature’ in a later stage, and how exciting changes can occur quite suddenly in fields thought to be mature and uninteresting.

Plug-and-play aqueous electrochemical atom transfer radical polymerization

‘Plug-and-play’ simplified electrochemical atom transfer radical polymerisation of PEGA480 under potentiostatic and galvanostatic conditions proceeds with very good control to conversions up to 83%.

Radical-induced cationic frontal polymerisation for prepreg technology

In this study, a new type of prepreg technology has been established using a dual curing system consisting of 1,6-hexanediol diacrylate (HDDA) and frontally polymerisable components based on the epoxide resin. The study of the polymerisation of HDDA revealed (tert-butylcyclohexyl)peroxydicarbonate (BCPC) as the most suitable radical thermal initiator. The presence of BCPC resulted in a fast radical polymerisation of HDDA and no cationic ring-opening reaction of the epoxy, which was observed by monitoring the double bond and epoxy group conversion in real time-NIR rheology measurement. The formed prepreg can subsequently be cured by radical-induced cationic frontal polymerisation of the epoxy resin. Effects of HDDA amount on the radical polymerisation, stiffness of the gel, frontal parameters and thermal mechanical properties of final polymers were investigated. With 10 wt% HDDA, the formed prepreg has very good storage stability, which was proved by monitoring the epoxy group conversion during 4 months of storage at 50 °C while still a stable front can be obtained. Furthermore, the RICFP-prepregs with different fibre contents were prepared and polymerised by RICFP. Then, a snowflake composite was successfully produced using RICFP-prepreg. Graphic abstract

Bromoform-assisted aqueous free radical polymerisation: a simple, inexpensive route for the preparation of block copolymers

In the quest for commercially relevant block copolymer additives, for which overall average molecular composition is key but molar mass distribution is of little importance, we present a straightforward, sulfur-...

In-Situ Thermosensitive Hybrid Mesoporous Silica: Preparation and the Catalytic Activities for Carbonyl Compound Reduction

In this study, free-radical polymerisation inside MCM-41 mesopores was examined to expose a construction route for a temperature-responsive switchable polymer-silica nanohybrid material with well-defined porosity. Herein, we introduced a vinyl...

Polymer Endgroup Control Through a Trifunctional Cobalt-Mediated Radical Polymerization: New Avenues for Synthesising Protein Conjugates

Cobalt-mediated radical polymerisations (CMRPs) have been initiated by the radical decarboxylation of tetrachlorophthalimide activated esters. This allows for the controlled radical polymerisation of both activated and less activated monomers across a broad temperature range with a single cobalt species, with incorporation of polymer endgroups derived from simple carboxylic acids derivatives and termination with an organozinc reagent. This method has been applied to the synthesis of a water-soluble protein/polymer conjugate, demonstrating the first example of CMRP in protein conjugation.

Fluorescent Imprinted Nanoparticles for the Effective Monitoring of Irinotecan in Human Plasma

Fluorescent, imprinted nanosized polymers for the detection of irinotecan have been synthesised using a napthalimide polymerisable derivative (2-allyl-6-[2-(aminoethyl)-amino] napthalimide) as functional monomer. The imprinted polymers contain ethylene glycol dimethacrylate (EGDMA) as a cross-linker and were prepared by high dilution radical polymerisation in dimethylsulphoxide (DMSO). The material was able to rebind irinotecan up to 18 nmol/mg with good specificity. Fluorescence emission at 525 nm (excitation at 448 nm) was quenched by increasing concentrations of irinotecan via a static mechanism and also in analytically useful environments as mixtures of human plasma and organic solvents. This allowed the direct detection of irinotecan (in the 10–30 μM range) in human plasma treated with acetonitrile; the limit of detection (LOD) was 9.4 nM, with within-run variability of 10% and day-to-day variability of 13%.